CN101225067B - Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane - Google Patents
Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane Download PDFInfo
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- CN101225067B CN101225067B CN2007100342812A CN200710034281A CN101225067B CN 101225067 B CN101225067 B CN 101225067B CN 2007100342812 A CN2007100342812 A CN 2007100342812A CN 200710034281 A CN200710034281 A CN 200710034281A CN 101225067 B CN101225067 B CN 101225067B
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- meng
- alkane
- metalloporphyrin
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- menthane
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Abstract
The invention discloses a method that menthane is catalyzed and oxygenated selectively by air into hydrogen peroxide p-menthane, which is characterized in that: the oxidant is air or oxygen-enriched air or oxygen; the pressure controlling the reaction is atmospheric pressure (at an atmospheric pressure); reaction temperature is 80 to 140 DEG C; Mu-oxygen-metalloporphyrin and single metalloporphyrin or the supported object of general formula (I) or (II) are selected as main catalyst with the concentration of 1 to 90 ppm; transition metal salts or oxide are used as co-catalyst; molar ration between the main catalyst and co-catalyst is 1: (0.5 to 5); reaction period is 1 to 10 hours; the reaction can be made at single constant temperature and also can be firstly made at constant temperature for one period before temperature is immediately decreased to certain temperature point for continuous reaction. The method that menthane is catalyzed and oxygenated selectively by air into hydrogen peroxide p-menthane has the advantages of short reaction period, high single-pass conversion rate upon menthane, good selectivity of hydrogen peroxide p-menthane, high recovery rate, high purity and easy separation and purification, and thus can avoid producing over-oxidation products.
Description
Technical field:
The present invention relates to a kind of to the Meng alkane be the method for hydrogen peroxide by air or oxygen-rich air selective catalytic oxidation to alkane in the Meng.
Background technology:
To the Meng alkane be important fine chemical product, generally obtain through the kautschin hydrogenation from afforestation product.Hydrogen peroxide is a kind of olefinic polymerization initiator of excellent performance to alkane in the Meng (being called for short PMHP), at present domestic main initiator as low temperature emulsion method polymerized sbr.To alkane in the Meng, is to obtain the important method of hydrogen peroxide to alkane in the Meng with air or oxygen-rich air oxidation.At present, industrial by to the Meng alkoxide to produce hydrogen peroxide be the non-catalyst oxidation technology to what the Meng, alkane adopted, under the temperature about 110-140 ℃, react usually, be oxygenant with the air, reaction times reached more than 30 hours, and hydrogen peroxide is about 20% to the productive rate of alkane in the Meng.Because long reaction time causes by product more.Because the per pass conversion of alkane is lower to the Meng, causes the raw material internal circulating load big, hydrogen peroxide is very big to the energy expenditure of alkane in the Meng in putting forward dense process.
Summary of the invention:
It is short to the purpose of this invention is to provide a kind of reaction times, to the Meng alkane per pass conversion height, to the Meng alkane hydrogen peroxide selectivity and productive rate all very high, to the Meng alkane prepare the novel method of hydrogen peroxide to alkane in the Meng.
The objective of the invention is to adopt following technical proposals to realize: feeding under atmospheric air or the oxygen-rich air condition, temperature of reaction is 80-140 ℃, select for use general formula (I) or μ (II)-oxygen bimetallic porphyrin and monometallic porphyrin or their immobilized thing as Primary Catalysts, Primary Catalysts concentration is 1-90ppm, as co-catalyst, the mol ratio of Primary Catalysts and co-catalyst is 1: (0.5-5) with transition metal salt or oxide compound. reaction times 1-10 hour.Metalloporphyrin can be efficient as biological enzyme under biological concentration, highly selective catalytic air or dioxygen oxidation to the Meng alkane be that hydrogen peroxide is to alkane in the Meng.The control of this temperature of reaction is very crucial, and under constant temperature, in the short reaction times, hydrogen peroxide reaches about 35% the high energy of productive rate of alkane in the Meng.Yet, adopt the another one temperature-controlled process, i.e. elder generation's initiation reaction for some time under comparatively high temps, cool to a certain temperature spot then immediately and continue reaction, under this temperature control condition, hydrogen peroxide can reach more than 39% the productive rate of alkane in the Meng.The blank reaction of no catalysis under the equal conditions, hydrogen peroxide has only about 18% the productive rate of alkane in the Meng.
Atoms metal M in the above-mentioned metal porphyrins structure, M
1, M
2It can be transition metal atoms; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, halogen, matrix, amino, glycosyl replaces glycosyl and cyclodextrin.Dentate X can be an acetate, acetate acetone, halogen.
Hydrogen peroxide of the present invention can be one or more of above-mentioned metalloporphyrin to the catalyzer among the Meng alkane preparation technology.Also can be above-mentioned metalloporphyrin and supported metalloporphyrin inorganic and that organic polymer constitutes by physics or chemical process.
The carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, titanium dioxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene etc.
Described transition metal salt or oxide compound as co-catalyst have: Cu, Zn, Fe, Co, Mn, Cr, Ni etc.These metal-salts or oxide compound can obviously improve metalloporphyrin to the catalytic performance of atmospheric oxidation to alkane in the Meng.
The composite catalyst that is made of metalloporphyrin or they and transition metal salt and oxide compound the results showed, to atmospheric oxidation to the Meng alkane become hydrogen peroxide to the Meng alkane reaction have good catalytic performance.With the variation of catalysis of metalloporphyrin agent composition and temperature of reaction, hydrogen peroxide to the Meng alkane transformation efficiency between 15-40%.Because lower and reaction times of temperature of reaction is short, effectively controlled to the Meng alkane deep oxidation and the further decomposition of superoxide.
Embodiment:
Embodiment 1:
With the metalloporphyrin that 2mg has general formula (I) structure, R
2=R
3=H, R
1=Cl, M=Mn, add 250ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.120 ℃ of following stirring reactions 4 hours, hydrogen peroxide was 15.8% to the productive rate of alkane in the Meng.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 4.1%.
Embodiment 2:
With the metalloporphyrin that 2mg has general formula (I) structure, R
2=R
3=H, R
1=Cl, M=Fe, add 250ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.120 ℃ of following stirring reactions 4 hours, hydrogen peroxide was 13.6% to the productive rate of alkane in the Meng.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 4.1%.
Embodiment 3:
With the metalloporphyrin that 5mg has general formula (II) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn, the 5mg manganese acetate, add 250ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.120 ℃ of following stirring reactions 5 hours, hydrogen peroxide to the Meng alkane productive rate be 19.7%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 5.8%.
Embodiment 4:
With the metalloporphyrin that 2mg has general formula (II) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn, add 250ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.Stirring reaction is 5 hours under 120C, hydrogen peroxide to the Meng alkane productive rate be 18.8%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 5.8%.
Embodiment 5:
With the metalloporphyrin that 3mg has general formula (II) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn, add 375ml in the Meng alkane, feeding normal pressure, contain oxygen with the flow of 500ml/min is 40% oxygen-rich air.120 ℃ of following stirring reactions 5 hours, hydrogen peroxide to the Meng alkane productive rate be 21.4%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 5.5%.
Embodiment 6:
With the metalloporphyrin that the immobilized 1.5mg of nano titanium oxide has general formula (I) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn, add 250ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.120 ℃ of following stirring reactions 4 hours, hydrogen peroxide to the Meng alkane productive rate be 17.5%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 4.1%.
Embodiment 7:
With the metalloporphyrin that 8mg has general formula (II) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn, add 260ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.120 ℃ of following stirring reactions 5 hours, hydrogen peroxide to the Meng alkane productive rate be 35.4%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 5.8%.
Embodiment 8:
With the metalloporphyrin that 8mg has general formula (I) structure, R
2=R
3=H, R
1=Cl, M
1=M
2=Mn, add 260ml in the Meng alkane, feed atmospheric air with the flow of 600ml/min.120 ℃ of following stirring reactions 4 hours, cool to 110 ℃ then immediately and continue reaction 3 hours, hydrogen peroxide to the Meng alkane productive rate be 39.6%.And the non-catalyst oxidation process that does not add metalloporphyrin with this understanding, hydrogen peroxide to the Meng alkane productive rate have only 16.8%.
Claims (5)
- A catalytic air oxidation to the Meng alkane prepare the method for hydrogen peroxide to alkane in the Meng, it is characterized in that feeding atmospheric air or oxygen-rich air or normal pressure oxygen, temperature of reaction is 80-140 ℃, select for use by general formula (I) or (II) metalloporphyrin make Primary Catalysts, the consumption of Primary Catalysts is 1-90ppm, make co-catalyst with transition metal salt or oxide compound, the mol ratio of Primary Catalysts and co-catalyst is 1: (0.5-5);
Atoms metal M in the above-mentioned metal porphyrins structure, M 1, M 2It can be transition metal atoms; Substituent R on the phenyl ring 1, R 2, R 3Can be hydrogen, alkyl, alkoxyl group, the alcoxyl hydroxyl, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin; Dentate X can be an acetate, methyl ethyl diketone, halogen. - A catalytic air oxidation to the Meng alkane prepare the method for hydrogen peroxide to alkane in the Meng, it is characterized in that feeding atmospheric air or oxygen-rich air or normal pressure oxygen, temperature of reaction is 80-140 ℃, select for use by general formula (I) or (II) metalloporphyrin make Primary Catalysts, the consumption of Primary Catalysts is 1-90ppm;
Atoms metal M shown in general formula (I), (II) in the metal porphyrins structure, M 1, M 2It can be transition metal atoms; Substituent R on the phenyl ring 1, R 2, R 3Can be hydrogen, alkyl, alkoxyl group, the alcoxyl hydroxyl, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin; Dentate X can be an acetate, methyl ethyl diketone, halogen. - 3. it is characterized in that according to claim 1 or 2 described methods: the catalysis of metalloporphyrin oxidizing reaction of alkane can be carried out under the constant temp condition to the Meng; Also can under a constant temp, react for some time earlier, drop to a certain temperature then and proceed reaction.
- 4. it is characterized in that according to claim 1 or 2 or 3 described methods: metalloporphyrin can constitute supported metalloporphyrin with following carrier: silica gel, molecular sieve, aluminum oxide, titanium dioxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, poly-peroxide ethene, polystyrene.
- 5. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that described transition metal salt or oxide compound can be the salt or the oxide compound of following metal: Cu, Zn, Fe, Co, Mn, Cr, Ni.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100342812A CN101225067B (en) | 2007-01-19 | 2007-01-19 | Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane |
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| CN2007100342812A CN101225067B (en) | 2007-01-19 | 2007-01-19 | Method for preparing hydroperoxidation p-menthane by catalytic air oxidation p-menthane |
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| CN101225067B true CN101225067B (en) | 2011-12-07 |
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| CN101962352B (en) * | 2010-09-17 | 2011-08-31 | 湖南松源化工有限公司 | Method for continuously producing p-menthane hydroperoxide by p-menthane and device thereof |
| CN102617415A (en) * | 2012-02-20 | 2012-08-01 | 常熟理工学院 | Reaction method capable of utilizing oxygen to oxidize organic sulfur compounds |
| CN106316911B (en) * | 2015-06-15 | 2018-06-12 | 华东理工大学 | Prepared by method and device of the hydrogen peroxide to Meng's alkane to Meng's alkane non-catalytic oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489716A (en) * | 1987-01-02 | 1996-02-06 | Sun Company, Inc. (R&M) | Reactions catalyzed by haloporphyrins |
| CN1850756A (en) * | 2006-05-22 | 2006-10-25 | 湖南大学 | Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane |
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2007
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489716A (en) * | 1987-01-02 | 1996-02-06 | Sun Company, Inc. (R&M) | Reactions catalyzed by haloporphyrins |
| CN1850756A (en) * | 2006-05-22 | 2006-10-25 | 湖南大学 | Technology and apparatus for preparing cyclohexanol, cyclohexanone and adipic acid by cyclohexane |
Non-Patent Citations (2)
| Title |
|---|
| 刘先章.对孟烷的氧化反应.林产化工通讯 1.1997,(1),6-9. |
| 刘先章.对孟烷的氧化反应.林产化工通讯 1.1997,(1),6-9. * |
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